EP2081925A1 - Benzoylpyrazole, ihre verwendung als herbizide, und zwischenprodukte - Google Patents

Benzoylpyrazole, ihre verwendung als herbizide, und zwischenprodukte

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Publication number
EP2081925A1
EP2081925A1 EP07818631A EP07818631A EP2081925A1 EP 2081925 A1 EP2081925 A1 EP 2081925A1 EP 07818631 A EP07818631 A EP 07818631A EP 07818631 A EP07818631 A EP 07818631A EP 2081925 A1 EP2081925 A1 EP 2081925A1
Authority
EP
European Patent Office
Prior art keywords
methyl
alkyl
formula
ethyl
tetrazol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP07818631A
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English (en)
French (fr)
Other versions
EP2081925B1 (de
Inventor
Shinichi Narabu
Yasushi Yoneta
Akihiko Yanagi
Shinichi Shirakura
Seiji Ukawa
Teruyuki Ichihara
Shin Nakamura
Martin Hills
Heinz Kehne
Jan Dittgen
Dieter Feucht
Christopher Rosinger
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer CropScience AG
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Bayer CropScience AG
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Publication of EP2081925A1 publication Critical patent/EP2081925A1/de
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Publication of EP2081925B1 publication Critical patent/EP2081925B1/de
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/713—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with four or more nitrogen atoms as the only ring hetero atoms

Definitions

  • the present invention relates to novel benzoylpyrazoles, their use as herbicides, to 0 process for their preparation and to their novel intermediates.
  • the present inventors have intensively studied to create novel compounds having higher efficacy as herbicides and being safer.
  • the present inventors !5 have found novel benzoylpyrazoles represented by the formula set forth below which exhibit superior herbicidal activity and safety against crops.
  • R 1 represents alkyl
  • R 2 represents alkyl or cycloalkyl
  • R 3 represents hydrogen, alkyl, alkenyl, alkynyl, aralkyl, alkylsulfonyl, optionally substituted phenylsulfonyl, acyl or acylalkyl;
  • X represents halogen or alkyl;
  • Y represents halogen
  • T represents a group T1 :
  • N N T (T2)
  • R 4 represents hydrogen, alkyl, alkoxy or alkylthio.
  • Preparation process (b) compounds of formula (I) wherein R 3 represents alkyl, alkenyl, alkynyl, aralkyl, alkylsulfonyl, optionally substituted phenylsulfonyl, acyl or acylalkyl:
  • R 1 , R 2 , X, Y, n and T are as defined above, with compounds represented by the formula (III): R 3 -L (III)
  • R 3 is as defined above and L represents halogen.
  • the benzoyl pyrazoles of the formula (I) provided by the present invention have a more potent herbicidal activity than the compounds described in the above prior art documents while exhibiting extremely superior efficacy as selective herbicides without substantially no phytotoxity to crops.
  • the benzoylpyrazoles of the formula (I) exhibit extremely superior efficacy as herbicides for Leguminous dry field crops such as soy beans and Poaceae dry field crops such as wheat, barley, oats and corn. Accordingly, the benzoylpyrazoles of the formula (I) of the present invention are particularly useful as herbicides for dry field.
  • halogen means fluorine, chlorine, bromine or iodine, and preferably chlorine and bromine.
  • alkyl may be those of a linear or branched chain, and means for example 0 C- I-6 alkyl. Specifically, examples of “alkyl” include methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl, n-, iso-, neo- or tert-pentyl, n- or iso-hexyl and the like.
  • cycloalkyl examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and the like. 5
  • alkenyl examples include allyl, 1-methylallyl, 1 ,1-dimethylallyl, 2-butenyl, 2-pentenyl, 2-hexenyl, 2-heptenyl and the like.
  • alkynyl examples include ethynyl, 2-propynyl, 1-methyl-2-propynyl, !0 1 ,1-dimethyl-2-propynyl, 2-butynyl, 2-pentynyl, 2-hexynyl, 2-heptynyl and the like.
  • aralkyl means, for example, an arylalkyl group the alkyl moiety of which has the above meaning, and the "aryl” means, for example, phenyl, naphthyl and the like, and specifically, benzyl.
  • alkoxy means, for example, an alkyl-O- group the alkyl moiety of which has the above meaning, and can be, for example, Ci -6 alkoxy. Specifically, . examples of “alkoxy” include methoxy, ethoxy, n- or iso-propoxy, n-, iso-, sec- or tert-butoxy, n-pentyloxy, n-hexyloxy and the like.
  • alkylthio means an alkyl-S- group the alkyl moiety of which has the above meaning, and can be, for example, Ci -6 alkylthio.
  • alkylthio include methylthio, ethylthio, n- or iso-propylthio, n-, iso, sec- or tert-butylthio, n-penthylthio, n-hexylthio and the like.
  • alkylsulfonyl means an alkyl-SO 2 - group the alkyl moiety of which has the above meaning, and can be, for example, d- 6 alkylsulfonyl.
  • alkylsulfonyl include methylsulfonyl, ethylsulfonyl, n- or iso-propylsulfonyl, n-, iso-, sec- or tert-butylsulfonyl, n-pentylsulfonyl, n-hexylsulfonyl and the like.
  • acyl is an acyl group derived from aliphatic saturated monocarboxylic acid, or aliphatic or aromatic hydrocarbon ring carboxylic acid, and means for example, a C- I-6 alkyl-CO- group the alkyl moiety of which has the above meaning, or an aryl-CO- group the aryl moiety of which is as defined above.
  • acyl include acetyl, propionyl, butyryl, isobutyryl, valeryl, isovaleryl, pivaloyl, n-pentylcarbonyl, n-hexylcarbonyl, benzoyl and the like.
  • Acylalkyl is an acylalkyl group the acyl and alkyl moieties of which have the above meaning, and means for example, a benzoyl-Ci_ 6 alkyl group, and specifically, includes phenacyl and the like.
  • a preferable group of compounds of the invention includes those of the formula (I), wherein
  • R 1 represents Ci -6 alkyl
  • R 2 represents Ci -6 alkyl or Ca -7 cycloalkyl
  • R 3 represents hydrogen, C 1-6 alkyl, C 3-7 alkenyl, C 3-7 alkynyl, C 7- i 2 aralkyl, Ci -6 alkylsulfonyl, optionally Ci -6 alkyl-substituted phenylsulfonyl, C- ⁇ - 6 alkyl-carbonyl, benzoyl or benzoyl-C- ⁇ -6 alkyl;
  • X represents halogen or Ci -6 alkyl
  • R 4 represents hydrogen, d- 6 alkyl, C- ⁇ - 6 alkoxy or Ci- 6 alkylthio.
  • a more preferable group of the compounds of the invention includes those of the formula (I) 1 wherein 5 R 1 represents methyl or ethyl;
  • R 2 represents methyl, ethyl or cyclopropyl
  • R 3 represents hydrogen, methyl, allyl, propargyl, benzyl, methanesulfonyl, n-propanesulfonyl, optionally methyl-substituted phenylsulfonyl, acetyl, benzoyl or phenacyl;
  • 0 X represents chlorine, bromine or methyl;
  • Y represents chlorine or bromine
  • n represents 2 or 3
  • T represents a group represented by
  • R 4 represents hydrogen, methyl, ethyl, methoxy or methylthio.
  • the compounds of the forrnuid (i) of the ⁇ iesent invention can exist as tautomers when R represents hydrogen, as shown by the following formulae (Ia), (Ib) and (Ic).
  • the compounds of the formula (II) used as raw materials in the above preparation process (a) are novel compounds not described in prior literatures. They may be prepared in accordance with the processes described in, for example, Japanese Patent KOKAI Publication No. 2-173 (hereinafter "Japanese Patent KOKAI Publication No.” is referred to as "JP-A-”), WO93/18031 and the like. Namely, they can be prepared by reacting compounds represented by the formula (IV):
  • Hal represents halogen, preferably chlorine or bromine, in the presence of a suitable acid coupling agent, for example, v-i Ii i ⁇ ii ⁇ y ⁇ m i ic ii i ⁇ ou u ⁇ uio u nuoi i i, iui c ⁇ u i ⁇ io, u ioi mji ⁇ j ⁇ n ⁇ ii iai ic.
  • a suitable acid coupling agent for example, v-i Ii i ⁇ ii ⁇ y ⁇ m i ic ii i ⁇ ou u ⁇ uio u nuoi i i, iui c ⁇ u i ⁇ io, u ioi mji ⁇ j ⁇ n ⁇ ii iai ic.
  • a part of the compounds represented by the above formula (V) are novel compounds not described in prior literatures and can be prepared in accordance with the processes described in literatures, for example, JP-A-2-173, WO93/18031 , WO03/66607 and the like. Namely, they can be prepared by reacting compounds
  • halogenating agents such as, for example, phosphorus oxychloride, phosphorus oxybromide, phosphorus trichloride, !0 phosphorus tribromide, phosgene, oxalyl dichloride, thionyl chloride and thionyl bromide.
  • a part of the compounds represented by the above formula (Vl) are novel compounds not described in prior literatures and can be prepared in accordance with !5 the processes described in literatures, for example, JP-A-2-173, WO03/66607 and the like. Namely, they can be prepared by hydrolyzing compounds represented by the formula (VII):
  • R 5 represents Ci -4 alkyl, preferably methyl or ethyl in the presence of a suitable base, for example, sodium hydroxide in 5 a diluent, for example, aqueous dioxane.
  • R 5 represents Ci -4 alkyl, preferably 5 methyl or ethyl
  • Hal represents halogen, preferably chlorine or bromine with the compounds represented by the formula (IX) T-H (IX)
  • T is as defined above, in the presence of a suitable condensing agent, for !0 example, potassium carbonate in a suitable diluent, for example, N,N-dimethylformamide.
  • a suitable condensing agent for !0 example, potassium carbonate
  • a suitable diluent for example, N,N-dimethylformamide.
  • Representative examples of the compounds of the formula (IV) used as raw materials in the preparation of the compounds of the above formula (II) include those described below. 1 ,3-Dimethyl-5-hydroxypyrazole, 1-methyl-3-ethyl-5-hydroxypyrazole, i-methyl-S-cyclopropyl- ⁇ -hydroxypyrazole, 1-ethyl-3-methyl-5-hydroxypyrazole, 5 i-ethyl-S-cyclopropyl- ⁇ -hydroxypyrazole, and etc.
  • Representative examples of the compounds of the formula (V) used as raw materials in the preparation of the compounds of the above formula (II) include those described below.
  • Representative examples of the compounds of the formula (Vl) used as raw materials in the preparation of the compounds of the above formula (V) include those described below.
  • Representative examples of the compounds of the formula (VIII) used as raw materials in the preparation of the compounds of the above formula (VII) include those described below.
  • Representative examples of the compounds of the formula (IX) used as raw materials in the preparation of the compounds of the above formula (VII) include those described below.
  • Representative examples of the compounds of the formula (Ia) used as raw materials in the preparation process (b) include those described below which are encompassed by the formula (I).
  • the compounds of the formula (III), which are raw materials in the above preparation process (b), are halogenated alkyl, halogenated alkenyl, halogenated alkynyl, halogenated aralkyl, halogenated acyl, halogenated sulfonyl and acylalkyl halide that are well known themselves in the field of organic chemistry, and those described below can be exemplified.
  • Methyl iodide propargyl bromide, benzyl bromide, n-propane sulfonyl chloride, 4-methylbenzene sulfonyl chloride, acetyl chloride, phenacyl bromide and etc.
  • the reaction of the above preparation process (a) can be carried out in a suitable diluent and examples thereof that may be used during the process include aliphatic, alicyclic and aromatic hydrocarbons (which may be optionally chlorinated), for example, pentane, hexane, cyclohexane, petroleum ether, ligroin, toluene, xylene, dichloromethane, 1 ,2-dichloroethane and etc;
  • ethers such as for example, ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF) and diethylene glycol dimethyl ether (DGM);
  • ketones such as for example, acetone, methyl ethyl ketone (MEK), methyl isopropyl ketone and methyl isobutyl ketone (MIBK);
  • nitriles such as for example, acetonitrile and propionitrile
  • alcohols such as for example, methanol, ethanol and isopropanaol
  • esters such as for example, ethyl acetate, amyl acetate
  • dimethylformamide DMF
  • DMA dimethylacetamide
  • N-methylpyrrolidone N-methylpyrrolidone
  • 1 ,3-dimethyl-2-imidazolidinone N-methylformamide (DMF)
  • DMF dimethylformamide
  • DMA dimethylacetamide
  • N-methylpyrrolidone N-methylpyrrolidone
  • sulfones and sulfoxifdes such as dimethylsulfoxide (DMSO) and sulfolane; and bases such as for example, pyridine.
  • DMSO dimethylsulfoxide
  • bases such as for example, pyridine.
  • the preparation process (a) can be carried out in the presence of a base.
  • a base includes, from inorganic bases, carbonates and bicarbonates of alkali metal and alkali earth metal such as for example, sodium bicarbonate, potassium bicarbonate, sodium carbonate and potassium carbonate; and from organic bases, tertiary amines, dialkylaminoanilines and pyridines such as for example, triethylamine, 1 ,1 ,4,4-tetramethylethylenediamine (TMEDA), N 1 N- dimethylaniline, N,N-diethylaniline, pyridine, 4-dimethylaminopyridine (DMAP) 1 1 ,4- diazabicyclo[2,2,2]octane (DABCO) and 1 ,8-diazabicyclo[5,4,0]undec-7-ene (DBU).
  • TEDA triethylamine
  • TEDA triethylamine
  • DMAP 4-dimethylamin
  • the preparation process (a) can be carried out in the presence of cyanide.
  • the catalysts include sodium cyanide, potassium cyanide, acetone cyanohydrin, hydrogen cyanide and the like.
  • a 0 diluent that may be used during the preparation include aliphatic, alicyclic and aromatic hydrocarbons (which may be optionally chlorinated), for example, pentane, hexane, cyclohexane, petroleum ether, ligroin, toluene, xylene, dichloromethane and the like;
  • ethers such as for example, ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF) and diethylene glycol dimethyl ether (DGM);
  • nitriles such as for example, acetonitrile and propionitrile. »0
  • phase-transfer catalysts examples include crown ethers such as for example, dibenzo-18-crown-6, dicyclohexyl-18-crown-6, 18-crown-6 and 15-crown-5.
  • the preparation process (a) can be carried out within a substantially wide range of >5 temperatures.
  • the suitable range of temperatures is between about 5°C to about 200 0 C and preferably about 25 0 C to about 130 0 C.
  • the reaction is conducted desirably under normal pressure, but it can also be operated under elevated JO pressure or reduced pressure.
  • a diluent for example, dioxane
  • the suitable range of temperatures is between about -10°C to about 80°C and preferably about 5°C to about 40 0 C.
  • the reaction is conducted 0 desirably under normal pressure, but it can also be operated under elevated pressure or reduced pressure.
  • the compounds of the formula (I) can be obtained by starting from the compounds of the formula (Vl) and continuously !0 carrying out one pot reaction without isolating the compounds of the formula (V) and those of the formula (II).
  • reaction of the above preparation process (b) can be carried out in a suitable diluent and examples thereof that may be used during the process include !5 water;
  • aliphatic, alicyclic and aromatic hydrocarbons which may be optionally chlorinated
  • ethers such as for example, ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF) and diethylene glycol dimethyl ether (DGM);
  • ketones such as for example, acetone, methyl ethyl ketone (MEK), methyl isopropyl ketone and methyl isobutyl ketone (MIBK);
  • nitriles such as for example, acetonitrile, propionitrile and acrylonitrile
  • esters such as for example, ethyl acetate and amyl acetate
  • amides such as for example, dimethylformamide (DMF), dimethylacetamide (DMA), N-methylpyrrolidone and 1 ,3-dimethyl-2-imidazolidinone, hexamethylphosphoric triamide (HMPA); 5 sulfones and sulfoxifdes such as for example, dimethylsulfoxide (DMSO) and sulfolane; and
  • bases such as for example, pyridine.
  • the preparation process (b) can be carried out in the presence of acid coupling agents.
  • the acid coupling agents include, from inorganic bases, hydrides, hydroxides, carbonates and bicarbonates of alkali metal and alkali earth metal such as for example,
  • pyridines such as for example, triethylamine, 1 ,1 ,4,4-tetramethylethylenediamine (TMEDA), N,N-dimethylaniline, N,N-diethylaniline, pyridine, 4-dimethylaminopyridine (DMAP), 1 ,4-diazabicyclo[2,2,2]octane (DABCO) and 1 ,8-diazabicyclo[5,4,0]undec-7-ene (DBU).
  • TEDA triethylamine
  • TEDA 1,1 ,4,4-tetramethylethylenediamine
  • DMAP 4-dimethylaminopyridine
  • DABCO 1 ,4-diazabicyclo[2,2,2]octane
  • DBU 1 ,8-diazabicyclo[5,4,0]undec-7-ene
  • the preparation process (b) can also be carried out by a process of using 5 phase-transfer catalysts.
  • a diluent that may be used during the preparation include
  • aliphatic, alicyclic and aromatic hydrocarbons which may be optionally chlorinated, for example, pentane, hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene,
  • dichloromethane chlorobenzene, dichlorobenzene and the like
  • 5 ethers such as for example, ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF) and diethylene glycol dimethyl ether (DGM);
  • nitriles such as for example, acetonitrile, propionitrile and acrylonitrile; and the like.
  • phase-transfer catalysts include quaternary ions such as for example,
  • crown ethers such as for example, dibenzo-18-crown-6, dicyclohexyl-i ⁇ -crown-6 and 18-crown-6;
  • cryptands such as for example, [2.2.2]-cryptate, [2.1.1]-cryptate, [2.2.1]-cryptate, [2.2.B]-cryptate, [2O2O2S]-cryptate and [3.2.2]-cryptate.
  • the preparation process (b) can be carried out within a substantially wide range of temperatures.
  • the suitable range of temperatures is between about -20 0 C to about 14O 0 C and preferably about 0 0 C to about 100 0 C.
  • the reaction is conducted desirably under normal pressure, but it can also be operated under elevated pressure or reduced pressure.
  • the active compounds of the formula (I) according to the present invention exhibit superior herbicidal activity for various weeds as shown in Biological Test Examples to be described later and can be used as herbicides.
  • weeds mean, in the broadest sense, all plants that grow in locations where they are undesired.
  • the compounds of the present invention act as selective herbicides depending on the application concentration.
  • the active compounds according to the present invention can be used, for example, between the following weeds and cultures.
  • Echinochlona Setaria, Panicum, 0 Digitaria, Phleum, Poa, Festuca, Eleusine, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Agrostis, Alopecurus, Cynodon, Commelina, Brachiaria, Leptochloa, and the like.
  • the use of the active compounds of the formula (I) of the present invention !0 is not limited to the above species of weeds but can also be applied to other species of weeds similarly.
  • active compounds of the present invention is not limited to the above plants but can also be applied to other plants similarly. Further, the active compounds of the present invention is not limited to the above plants but can also be applied to other plants similarly. Further, the active compounds of the present invention is not limited to the above plants but can also be applied to other plants similarly. Further, the active compounds of the present invention is not limited to the above plants but can also be applied to other plants similarly. Further, the active compounds of the present invention is not limited to the above plants but can also be applied to other plants similarly. Further, the active
  • !5 compounds of the present invention can non-selectively control weeds and can be used, for example, in industrial areas such as factories, railway tracks, roads, plantations, non plantation and the like, depending on the application concentration.
  • the compounds can also be used for controlling weeds in perennial plant cultivation such as, for example, afforestations, decorative tree plantings, orchards,
  • the compounds of the present invention can also be applied for selectively controlling weeds in annual plant cultivation.
  • the active compounds of the present invention can be made into the customary formulations for actual use. Examples of the formulation forms include solutions, wettable powders, emulsions, suspensions, dusts, water-dispersible granules, tablets, 5 granules, suspended emulsifiable concentrates, microcapsules in a polymer substance and etc.
  • formulations can be produced by known methods per se. For example, they can be prepared by mixing the active compounds with extenders, namely, liquid or 0 solid diluents or carriers and, optionally, with surfactants, namely, emulsifiers and/or dispersants and/or foam formers.
  • extenders namely, liquid or 0 solid diluents or carriers
  • surfactants namely, emulsifiers and/or dispersants and/or foam formers.
  • liquid diluents or carriers examples include aromatic hydrocarbons (for example, xylene, toluene, alkylnaphthalene and the like), chlorinated aromatic
  • hydrocarbons or chlorinated aliphatic hydrocarbons for example, chlorobenzenes, ethylene chlorides, methylene chloride and the like
  • aliphatic hydrocarbons for example, cyclohexane and the like, paraffins (mineral oil fractions and the like)]
  • alcohols for example, butanol, glycol and the like
  • ethers and esters thereof ketones (for example, acetone, methyl ethyl ketone, methyl isobutyl ketone,
  • strongly polar solvents for example, dimethylformamide, dimethylsulfoxide and the like
  • water etc.
  • organic solvents can be used as auxiliary solvents.
  • solid diluents may include ground natural minerals (for example, kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth) and ground synthetic minerals (for example, highly dispersed silicic acid, alumina and silicate).
  • ground natural minerals for example, kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth
  • ground synthetic minerals for example, highly dispersed silicic acid, alumina and silicate.
  • the solid carriers for granules may include crushed and fractionated rocks (for example, calcite, marble, pumice, sepiolite and dolomite), synthetic granules of inorganic or organic powders, and organic materials (for example, sawdust, coconut shells, maize cobs and tobacco stalks).
  • the emulsifiers and/or foam formers may include nonionic and anionic emulsifiers [for example, polyoxyethylene fatty acid esters, polyoxyethylene fatty acid alcohol ethers (for example, alkylaryl polyglycol ether), alkyl sulfonates, alkyl sulfates and aryl sulfonates] and albumin hydrolysates.
  • the dispersants include lignin sulfite waste liquor and methylcellulose.
  • Binders may also be used in the formulations (powders, granules and emulsifiable concentrates).
  • examples of the binders may include carboxymethyl cellulose, natural or synthetic polymers (for example, gum arabic, polyvinyl alcohol and polyvinyl acetate).
  • Colorants may also be used.
  • the colorants may include inorganic pigments (for example, iron oxide, titanium oxide and Prussian blue), organic colorants such as Alizarin colorants, azo colorants or metal phthalocyanine colorants, and further, trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum or zinc.
  • the formulations can contain the active compounds of the formula (I) in a range of generally 0.1 to 95% by weight and preferably 0.5 to 90% by weight.
  • the active compounds of the formula (I) of the present invention can be used for controlling weeds as such or in their formulation forms.
  • the active compounds of the formula (I) of the present invention can be used also in combination with known herbicides.
  • a mixed herbicide composition with known herbicides may be previously prepared as a final formulation form, or can be prepared by tank-mixing on occasion of application.
  • herbicides shown in common names can be exemplified as specific examples of herbicides that can be used in combination with the active compounds of the formula (I) of the present invention.
  • Sulfonylurea type herbicides for example, chlorsulfuron, sulfometuron methyl, chlorimuron ethyl, triasulfuron, amidosulfuron, oxasulfuron, tribenuron ethyl, prosulfuron, ethametsulfuron methyl, triflusulfuron methyl, thifensulfuron methyl, flazasulfuron, rimsulfuron, nicosulfuron, flupyrsulfuron, bensulfuron methyl, 5 pyrazosulfuron ethyl, foramsulfuron, sulfosulfuron, cinosulfuron, azimsulfuron, metsulfuronmethyl, halosulfuron methyl
  • carbamate type herbicides for example, phenmedipham, chloropropham, asulam, 0 bentiocarb, molinate, esprocarb, pyhbuticarb, dimepiperate and swep;
  • chloroacetanilide type herbicides for example, propachlor, metazachlor, alachlor, acetochlor, metolachlor, butachlor, pretilachlor and thenylchlor;
  • diphenylether type herbicides for example, acifluorfen, oxyfluorfen, lactofen, fomesafen, aclonifen, chlomethoxynyl, bifenox and CNP;
  • thazine type herbicides for example, simazine, atrazine, propazine, cyanazine, ametryn, simetryn, dimethametryn and prometrin;
  • phenoxy acid or benzoic acid type herbicides for example, 2,3,6-TBA, dicamba, quinclorac, quinmerac, clopyralid, picloram, triclopyr, fluroxypyr, fenoxaprop, diclofop methyl, fluazifop butyl, haloxyfop methyl, quizalofop ethyl, cyhalofop butyl, 2,4-PA, MCP, MCPB and phenothiol;
  • !5 acid amide or urea type herbicides for example, isoxaben, diflufenican, daiuron, linuron, fluometuron, difenoxuron, methyldymron, isoproturon, isouron, tebuthiuron, methabenzothiazuron, propanil, mefenacet, chlomeprop, naproanilide, bromobutide, daimuron, cumyluron, etobenzanid and oxadichlomefon;
  • SO organic phosphorous type herbicides for example, glyphosate, bialaphos, glufosinate, amiprophos methyl, anilophos, bensulide, piperophos and butamiphos; dinitroaniline type herbicides: for example, trifluralin and prodiamine;
  • phenolic type herbicides for example, bromoxynil, ioxynil and dinoseb;
  • cyclohexanedione type herbicides for example, alloxydim, sethoxydim, cloproxydim, clethodim, cycloxidim and tralkoxydim;
  • imidazolinone type herbicides for example, imazametabenz, imazapyr, imazamethapyr, imazethapyr, imazamox and imazaquin;
  • bipyridium type herbicides for example, paraquat and diquat;
  • carbamoyltetrazolinone type herbicides for example, fentrazamide
  • nitrile type herbicides for example, dichlobenil
  • herbicides for example, bentazone, tridiphane, indanofan, amitrol, carfentrazon ethyl, sulfentrazon, fenchlorazol ethyl, isoxaflutole, clomazone, maleic acid hydrazide, pyridate, chloridazon, norflurazon, pyrithiobac, bromacil, terbacil, metribuzin, oxaziclomefone, cinmethylin, flumiclorac pentyl, flumioxadin, fluthiacet methyl, azafenidin, benfuresate, oxadiazon, oxadiargyl, pentoxazone, cafenstrole, pyriminobac, bispiribac sodium, pyribenzoxim, pyriftalid, pyraflufen ethyl, benzobicyclon, dithiopyr, dalapon, and chlorthia
  • the active compounds of the formula (I) of the present invention can be also mixed with safeners to reduce phytotoxicity and to provide wider weed-controlling spectrum by the mixing, thereby their application as selective herbicides can be broadened.
  • safeners the following compounds shown in common names or development codes can be mentioned;
  • the mixed herbicide compositions comprising the active compounds of the formula (I) of the present invention and the above herbicides can be further mixed with the above safeners to reduce phytotoxicity and to provide wider weed- 5 control spectrum by the mixing, thereby their application as selective herbicides can be broadened.
  • the active compounds of the formula (I) of the present invention can be directly used as such or used in formulation forms such as formulated solutions for spraying, emulsifiable concentrates, tablets, suspensions, powders, >5 granules or used in the use forms prepared by further dilution.
  • the active compounds of the present invention can be applied, for example, watering, spraying, atomizing, scattering granules, and etc.
  • the active compounds of the formula (I) of the present invention can be used at any JO stage before and after germination of plants. Further, they can be also taken into the soil before sawing.
  • the application amount of the active compounds of the formula (I) can vary and fundamentally differs depending on the nature of the desired effect. In case of using the active compounds as herbicides, examples of the application amount, in terms of the active compounds, can be in the range of about 0.005 to about 4 kg per 5 hectare and preferably about 0.01 to about 2 kg per hectare.
  • T1 represents a group: R 4
  • Me represents methyl
  • Et represents ethyl
  • Pr-n represents n-propyl
  • cyclo-Pro represents cyclopropyl
  • OMe methoxy
  • SMe represents methylthio
  • SO 2 Me represents methanesulfonyl (methylsulfonyl)
  • Ph represents phenyl
  • Ph-4-Me represents 4-methylphenyl.
  • Emulsifier Benzyloxy polyglycol ether 1 part by weight
  • a suitable formulation of an active compound is obtained as an emulsifiable concentrate by mixing 1 part by weight of the active compound with the stated amounts of the carrier and emulsifier. A prescribed amount of the formulation is diluted with water.
  • Clay mineral particles (95 parts) having particle size distribution of 0.2-2 mm are charged in a rotary mixer, Compound No.14 (5 parts) of the present invention was sprayed together with a liquid diluent under rotation, wetted uniformly and then dried 5 at 40-50°C to obtain granules.
  • Compound No.104 (20 parts) of the present invention, sodium ligninsulfonate (30 parts), bentonite (15 parts) and calcined diatomaceous earth powder (35 parts) are well mixed, water was added thereto and the mixture was extruded with a screen of 0.3 mm and dried to obtain water-dispersible granules.

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Agronomy & Crop Science (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)
EP07818631A 2006-10-13 2007-10-02 Benzoylpyrazole, ihre Verwendung als Herbizide, und Zwischenprodukte Not-in-force EP2081925B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2006279533A JP5209194B2 (ja) 2006-10-13 2006-10-13 ベンゾイルピラゾール類及び除草剤
PCT/EP2007/008551 WO2008043456A1 (en) 2006-10-13 2007-10-02 Benzoylpyrazoles, their use as as herbicides, and intermediates

Publications (2)

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EP2081925A1 true EP2081925A1 (de) 2009-07-29
EP2081925B1 EP2081925B1 (de) 2012-02-15

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US (1) US8084398B2 (de)
EP (1) EP2081925B1 (de)
JP (1) JP5209194B2 (de)
KR (1) KR20090068275A (de)
CN (1) CN101522663A (de)
AR (1) AR063254A1 (de)
AT (1) ATE545643T1 (de)
AU (1) AU2007306726A1 (de)
BR (1) BRPI0717748B1 (de)
CA (1) CA2666347A1 (de)
CL (1) CL2007002960A1 (de)
CO (1) CO6160268A2 (de)
EA (1) EA015425B1 (de)
TW (1) TW200821300A (de)
WO (1) WO2008043456A1 (de)

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CN112409263B (zh) * 2019-08-23 2024-04-05 东莞市东阳光农药研发有限公司 取代的苯甲酰类化合物及其应用

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JPS61257974A (ja) 1985-05-11 1986-11-15 Nissan Chem Ind Ltd ピラゾ−ル誘導体，その製造方法および選択性除草剤
KR0149499B1 (ko) 1988-11-18 1998-10-15 디렉 콘스웨이트 삼중치환 벤조산 중간체
WO1993018031A1 (fr) * 1992-03-03 1993-09-16 Idemitsu Kosan Co., Ltd. Derive de pyrazole
JPH06247891A (ja) 1993-02-25 1994-09-06 Hokko Chem Ind Co Ltd シクロヘキサンジオン誘導体および除草剤
JPH07206808A (ja) 1994-01-17 1995-08-08 Hokko Chem Ind Co Ltd シクロヘキサンジオン誘導体および除草剤
JPH10109976A (ja) 1996-04-26 1998-04-28 Ishihara Sangyo Kaisha Ltd ピラゾール系化合物、それらの製造方法及びそれらを含有する除草剤
DE10039723A1 (de) * 2000-01-17 2001-07-19 Bayer Ag Substituierte Arylketone
BR0013075A (pt) * 1999-08-10 2002-05-21 Bayer Agrochem Kk Derivados de tetrazolinona
DE19953136A1 (de) * 1999-11-04 2001-05-10 Aventis Cropscience Gmbh Benzoylcyclohexandione und Benzoylpyrazole, Verfahren zu ihrer Herstellung und ihre Verwendung als Herbizide und Pflanzenwachstumsregulatoren
BR0107624A (pt) * 2000-01-17 2002-11-12 Bayer Ag Arilcetonas substituìdas
JP2003238540A (ja) * 2002-02-08 2003-08-27 Bayer Ag テトラゾール誘導体及び除草剤
DE10235945A1 (de) * 2002-08-06 2004-02-19 Bayer Cropscience Gmbh 3-Aminocarbonyl substituierte Benzoylpyrazolone

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CA2666347A1 (en) 2008-04-17
JP5209194B2 (ja) 2013-06-12
CN101522663A (zh) 2009-09-02
US8084398B2 (en) 2011-12-27
CL2007002960A1 (es) 2008-03-14
BRPI0717748A2 (pt) 2013-10-22
JP2008094771A (ja) 2008-04-24
US20100094023A1 (en) 2010-04-15
WO2008043456A1 (en) 2008-04-17
EP2081925B1 (de) 2012-02-15
EA015425B1 (ru) 2011-08-30
AR063254A1 (es) 2009-01-14
BRPI0717748B1 (pt) 2014-12-02
CO6160268A2 (es) 2010-05-20
KR20090068275A (ko) 2009-06-25
EA200900442A1 (ru) 2009-10-30
TW200821300A (en) 2008-05-16
AU2007306726A1 (en) 2008-04-17
ATE545643T1 (de) 2012-03-15

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